The method of producing catalyst for stereospecific polymerization of propylene
(57) Abstract:The inventive catalyst is produced by the interaction of the complexes of titanium tetrachloride with ether and diethylaluminium with ether in a hydrocarbon solvent consisting of alkanol and toluene or cyclohexane in an amount of not less than 5 vol.% these cyclic hydrocarbons by uniform dosing of a solution of a complex of diethylaluminium with ether into a solution of a complex of titanium tetrachloride with ether. 5 C. p. F.-ly, 1 table. The invention relates to methods of producing catalysts for stereospecific polymerization based on titanium trichloride.A known method of producing catalyst based on titanium trichloride  in three stages:
recovery TiCl4alyuminiiorganicheskikh connection at a low temperature;
processing of the received modification brown TiCl3simple ether;
heat treatment of the resulting product in the presence of TiCl4.This method for the first time made it possible to obtain a catalyst with high activity, high stereospecificity and morphology of the powder of the obtained polymer. The disadvantages of this SPO is th thermal stability of the catalyst during storage.Later, there were numerous patents that describe in more simple ways of receiving such catalysts in two or one stage.One example of such method is described in  According to this method, the catalyst prepared by the interaction of the titanium tetrachloride with complex alyuminiiorganicheskikh connection (for example, diethylaluminium) with aliphatic ether (for example, diazolinum). The interaction is carried out at temperatures from -10 to 60aboutWith a small ratio of TiCl4/Al-R 1.8 and the ratio of aliphatic ether/AlEt2Cl 2-5. The resulting precipitate is then maintained at 20-100aboutC for 1-24 hours One of the disadvantages of this method of cooking is that it does not allow regulation of the particle size in a fairly wide area.Despite the large number of ways to get TiCl3only in a small number of patents the possibility of regulating the size of the catalyst particles. It should be noted that the size and shape of catalyst particles determine the size and shape of the particles formed on the polymer according to the known phenomenon of replication catalyst particles in increasing her polymer particle. Regulirovanie the and improves the washing of residual catalyst and drying of solvent (suspension process). At the same time, the emergence of a very small fraction of the polymer is undesirable due to its entrainment by centrifugation of the suspension polymer and drying the polymer, and also because of its slidenote in the case of the production of the block copolymer. Therefore a number of different methods of polymerization and obtain various arches of the polymer should be of the optimum size of the polymer particles, which is achieved by regulating the size of the catalyst particles. The following describes a number of known ways in which the possibility of regulating the particle size of the catalyst.There is a method of preparation of the catalyst  by restoring TiCl4alyuminiiorganicheskikh compound in the presence of aliphatic ether and ganodermataceae connection, for example, chlorobenzene, 1,2,4-trichlorobenzene, etc. This method allows you through changing the content ganodermataceae connection to adjust the size of the catalyst particles in a wide range from 10 to 1000 μm. The disadvantage of this method is the low bulk density of the obtained polymer 0.24 to 0.32 g/cm3.Known more complicated way by the same authors  in which along with the use of haloaromatic compounds applied methods of temperature is the temperature value TiCl4, dibutylamino ether and diethylaluminium in the environment of a mixture of chlorobenzene and hexane, twice is a heating system with a certain speed to 60aboutWith subsequent rapid cooling to 20aboutC. When cooled system add a mixture of TiCl4and dibutylamino ether. Then the reaction system is heated to 80aboutC and maintained at this temperature for 1 h In the result catalysts with an average particle size of 40-400 mm, which allow to obtain a powder of polypropylene with higher bulk weight of 0.40-0.45 g/cm3. The disadvantages of this method are the relatively low activity (75-93 GPP/(g cat h ATM)), low bulk density of the polymer and complex synthesis technique.The closest in technical essence to the present invention is a method of obtaining titanium trichloride recovery TiCl4alyuminiiorganicheskikh compound in the presence of a simple air in the environment of aliphatic hydrocarbons [2,5-prototype] In this way the adjustment of the average particle size of the catalyst is from 10 to 43 μm by changing the content of air in the system and redistribution of the content broadcast in mixtures with TiCl4and AlEt2Cl. atcom of this method is that, when the reduction in the average size of the particles is strongly reduced bulk density of the obtained polymer. Thus, in examples 5 and 12 of the prototype  with an average particle size of the catalyst 10 and 15 microns bulk density of the polymer was between 0.30 and 0.40 g/cm3, respectively, which does not meet the requirements of industrial use. Only for catalysts with an average particle size 24-43 microns bulk density of the polymer has a satisfactory performance of 0.44-0,49 g/cm3[2,5]
The aim of the invention is to obtain a catalyst for propylene polymerization with controlled particle size below 20 microns, which allows to obtain a polymer with a high bulk weight. Found that, during the interaction of essential complexes TiCl4and AlEt2Cl in the environment of a mixed solvent consisting of aliphatic hydrocarbon (hereinafter alkane) and toluene or cyclohexane, it is possible to adjust the average particle size of the catalyst is in the range of 6-23 μm maintain high bulk weight of the obtained polymer. When this catalyst has high activity and a high stereospecificity. This objective is achieved in that the catalyst for the stereospecific polymerization of propylene is produced by inter who eat the interaction of these complexes is carried out in a medium of hydrocarbon solvent, consisting of alkanes and toluene or cyclohexane in an amount not less than about 5. these cyclic hydrocarbons, by uniform dosing of a solution of a complex of diethylaluminium with ether into a solution of a complex of titanium tetrachloride with ether.As ether is preferably used dietarily ether.In the complexes molar ratio of ether to titanium tetrachloride is 0.1-0.5, and the molar ratio of ether to diethylaluminium is 0.6 to 2.0.The interaction of these complexes is carried out in a period of 2-10 hours at a temperature of 25-40aboutWith subsequent exposure system at a temperature of 80-110aboutC.Toluene or cyclohexane is used for preparing a solution of a complex of titanium tetrachloride with ether or complex diethylacetanilide with ether or both of these complexes, with a total content of toluene or cyclohexane in a hydrocarbon solvent over 5%
The content of toluene or cyclohexane in the hydrocarbon mixture is preferably from 5 to about 60.Distinctive features of the process of preparation of the catalyst according to the invention are the use of the solvent mixture is RA complex diethylacetanilide with ether into a solution of a complex of titanium tetrachloride with ether.The catalyst according to the invention was prepared as follows. Prepare solutions of complex TiCl4with ether and AlEt2Cl and ether mixed solvent containing alkane and toluene or cyclohexane, at a content of toluene or cyclohexane solvent is more than about 5. The solution of complex TiCl4ether is loaded into the reactor, heated to 25-40aboutAnd then into the reactor under stirring for 3-10 h dispense the solution of complex AlEt2Cl with ether. At the end of the dosing reaction system is maintained at a temperature dosage for 0-1 h, then increase the temperature within 2-4 hours before 80-110aboutC and maintained at this temperature for 2-3 hours After deposition of sediment mother liquor is decanted and the catalyst was washed several times hydrocarbon solvent (hexane, heptane).The catalyst obtained according to the invention has a high activity 133-165 GPP/(g Kutch ATM) and high stereospecificity more than 96% of the Average particle size of the catalyst can be adjusted in the range of 6-23 μm by the interaction of the ether complexes TiCl4and AlEt2Cl in the environment combined solvent. The average particle size of the polymer at the exit 2 CCPR/g cat. ISM is aklanon reactor prepare a solution of the complex TiCl4with vitaminosis ether (DIAE) in toluene, sequentially loading 46 ml of toluene, 48,2 ml of TiCl4and 31 ml DIEA. To this solution at 35aboutWith and with constant stirring for 4 h dispense the solution of the complex of 15.5 ml of diethylacetanilide (DEAH) with 31 ml DIEA in 103 ml of heptane. The percentage of toluene in the total mixture of the solvent is about 31. After dosing, the reaction medium is stirred at 35aboutC for 1 h, then heated to 90aboutC for 3 h and maintained at that temperature for 2 hours Solid product advocate, decanted liquid phase and the solid phase is washed 5 times with 150 ml of heptane. Get the catalyst with an average particle size of 10 microns.The catalyst test carried out as follows. In the autoclave of 1 l at 25-30aboutTo give 250 ml of hexane, 0.24 g DEAH, 100 ml of hydrogen to 0.032 g of the obtained catalyst. Raise the pressure of propylene to 6 MPa and temperatures up to 70aboutC. After 2 h the contents of the autoclave was discharged and filtered. Get to 60.6 g of powder of polypropylene (PP). From the hexane after evaporation secrete soluble fraction of the polymer in the amount of 0.94 g (atactic polypropylene). The polymer has an average particle size d50 equal to 165 μm, and a bulk density 0,482 g/spolier shown in the table. Here for correct comparison of the sizes of particles of the catalyst are given the values of the average particle size of GD, reduced to one and the same polymer yield equal to 2 kg per 1 g of the catalyst (d50Pref). This value is obtained according to the equation:
d50Prefd50(2000/G)1/3where g polymer yield in grams of PM per 1 g of catalyst.P R I m m e R 2 (comparative). Receiving catalyst and carrying out the polymerization were carried out as in example 1, but for solution of complex TiCl4with ether instead of toluene using 46 ml of heptane. Get the catalyst with an average particle size of 20 microns.P R I m e R 3. The catalyst was prepared analogously to example 1, but in combination with titanium tetrachloride used 26 ml DEAE and 72 ml of toluene and, in combination with 13.3 ml DEAH used 26 ml DEAE and 54 ml of heptane. Stage batching complex DEAH with ether is carried out at 25aboutC.P R I m e R 4. The catalyst is prepared analogously to example 1, but in combination with TiCl4as a solvent used in 46 ml of a mixture of heptane to toluene when the content of toluene 50. and the temperature of the dispensing complex DEAH with ether and stirring the reaction medium at the end to the CNS with TiCl4used to 17.3 ml DEAE and in complex with DEAH 44,7 ml DIEA. As solvents for both complexes used a mixture of heptane to toluene when the content of toluene 25 about.P R I m e R 6. The catalyst is prepared analogously to example 5, but in combination with TiCl4as a solvent used in 60 ml of toluene, and in complex with DEAH 90 ml of heptane. The average particle size of the catalyst was 13.5 μm.P R I m e R 7 (comparative). The catalyst is prepared analogously to example 6, but in combination with TiCl4as the solvent used 60 ml of heptane. The conditions of this comparative example are consistent with the terms of the prototype (example 4, reference ). Get the catalyst with an average particle size of 28 μm.P R I m e R 8. The catalyst is prepared analogously to example 6, but in combination with TiCl4as the solvent used 60 ml of cyclohexane.P R I m e R 9. The catalyst is prepared analogously to example 8, but in combination with TiCl4the solvent used is a mixture of 30 ml of cyclohexane and 30 ml of heptane. The average particle size of the catalyst was 23 μm.P R I m e R 10. The catalyst is prepared analogously to example 9, but in combination with DEAH instead of heptane as dissolve theP R I m e R 11. The catalyst is prepared as in example 8, but for the preparation of the complex ester with DEAH used 90 ml of cyclohexane, and the holding temperature is 80aboutC.P R I m e R 12. The catalyst is prepared analogously to example 10, but in combination with TiCl4use of 8.9 ml DEAE and in complex with DEAH of 51.1 ml DIEA.P R I m e p 13. The catalyst is prepared analogously to example 1, but in combination with TiCl4use 44,6 ml DIEA, in combination with DEAH of 15.2 ml DEAE, and the solvent of the complex using heptane fraction containing toluene 5 about.P R I m e R 14. The catalyst is prepared analogously to example 6, but for solution of complex TiCl4with the use ether heptane, and for solution of complex DEAH with ether, a mixture of 60 ml of toluene and 30 ml of heptane. The percentage of toluene in the total mixture of the solvent is 40% as in example 6.P R I m e R 15. In a reactor with a volume of 3.2 m3download 240 l TiCl4, 180 l of toluene, 180 l of heptane fractions containing toluene 5 about. and 130 l DIAA. A solution of the obtained complex is heated to 35aboutC. In a reactor with a volume of 0.6 m3prepare a solution of the complex 72 kg TEACH and 130 l DEAE 256 l heptane fractions 8 h to a solution of the complex of TiCl4 with DEAE 35aboutC. At the end of dosing, the reaction mixture was stirred at 35aboutC for 1 h, then heated for 3 h to 90aboutC and maintained at that temperature for 2 hours Then the stirring is discontinued, the solid product is deposited, and the liquid phase decanted from the reactor. The solid product is washed several times heptane fraction and receive a suspension of the catalyst.In the autoclave of 1.5 l in the current propylene loaded 1 l of heptane fractions, 2 g DEAH and 0.07 g of the obtained catalyst. In the autoclave is introduced 200 ml of hydrogen, the pressure of propylene and the temperature in the reactor rises to 5.5 MPa and 70aboutC, respectively. After 5 hours of polymerization discharged from the autoclave and filtered 341 g of PP powder, which has an average particle size of 245 μm and bulk density 0,481 g/cm3. The amount of atactic polymer was 6.5 gP R I m e R 16. The catalyst prepare and test as in example 15, but for solution of complex TiCl4with DEAE use 360 l of toluene, and the holding temperature is 100aboutC. Obtain a catalyst with an average particle size of 65 μm.P R I m e R 17. The catalyst is prepared analogously to example 15, but for cooking RAZR with an average particle size of 19 μm.The given examples show that the introduction of the solvent is toluene or cyclohexane already in small amounts (15-20% other 4 and 9) can significantly reduce the average particle size of the catalyst and, accordingly, the polymer compared with the examples, when the solvent is used only alkane (comparative Ave 2 and 7 according to the prototype). The higher the content of toluene or cyclohexane, the smaller the particle size of the obtained polymer. The high content of toluene (60%) average particle size of the polymer is 100-130 μm, 2.7-3.3 times lower than in the absence of toluene (3, 16, etc. 2). It is important to note that while reducing the size of the catalyst particles less than 15 microns (for example, 1, 6, 17) bulk density of the polymer has a high value, while, according to well-known solution  while reducing the size of the catalyst particles to 10-15 microns bulk density of the polymer is significantly reduced (example 5 and 12 of the prototype ). The data given in the table. 1. The METHOD of producing CATALYST for STEREOSPECIFIC POLYMERIZATION of PROPYLENE by the interaction of the complexes of titanium tetrachloride with ether and diethylaluminium with ether in a hydrocarbon solvent, characterized in that the interaction yatasana with content of not less than 5 vol.%, by uniform dosing of a solution of a complex of diethylaluminium with ether into a solution of a complex of titanium tetrachloride with ether.2. The method according to p. 1, characterized in that the ether used as dietarily ether.3. The method according to p. 1, characterized in that the complexes molar ratio of ether to titanium tetrachloride is 0.1-0.5, and the molar ratio of ether to diethylaluminium - 0,6 - 2,0.4. The method according to p. 1, wherein toluene or cyclohexane is used for preparing a solution of a complex of titanium tetrachloride with ether or complex diethylacetanilide with ether or both of these complexes with the General content of toluene or cyclohexane in the hydrocarbon solvent is not less than 5%.5. The method according to p. 1, characterized in that the interaction of these complexes is carried out for 2 to 10 h at 25 - 40oWith subsequent exposure system at 80 - 110oC.6. The method according to p. 1, characterized in that the content of toluene or cyclohexane in the hydrocarbon mixture is 5 to 70 vol.%.
FIELD: chemistry of metalloorganic compounds, chemical industry.
SUBSTANCE: invention relates to preparing compounds of tetrapyrazinoporphyrazine order, namely, to cobalt octasulfooctaphenyltetrapyrazinoporphyrazine of the formula:
that can be used as a catalyst in oxidation reactions of sulfur-containing compounds, in particular, cysteine and thioureas, and diethylamine also being both in acid and neutral media.
EFFECT: valuable properties of compound.
2 cl, 2 dwg, 4 ex
FIELD: chemistry, pharmacology.
SUBSTANCE: present invention relates to method for production of indolo-pyrrolo-carbazole derivative according to formula (I) , or its pharmaceutically acceptable salt, that have antitumour activity. Invention also relates to method for production of indole compound according to formula (XII) , or its pharmaceutically acceptable salt, where R1 is protective hydroxy-group, distinguished by conducting interreaction between compound with formula (XIII) , or its pharmaceutically acceptable salt, where R1 is definitely above, Ra and Rb are either separately C1-C7-alkyl, or together form C3-C6-alkylene group, and hydrogen gas at 1 to 5 atmospheres, in presence of hydrogenation catalyst (applied as novel catalyst as well), which consist of rhodium compound, metal compound, and optionally amine, in inert solvent at room temperature; the rhodium compound being 1 to 10% rhodium on carbon, aluminium oxide, calcium carbonate, or barium sulphate, and metal compound being nickel (II), iron (II), iron (III), cobalt (II), or cobalt (III). Method is also submitted for production of bis-indole compound by formula (VIII) , or its pharmaceutically acceptable salt, where R1 is protective hydroxy-group, Y is hydrogen, C1-C7-alkyl, phenyl, benzyloxymethyl, or C7-C12-aralkyl, consisting in reaction of indole compound by formula (XII), or its pharmaceutically acceptable salt, where R1 is protective hydroxy-group, with ethylmagnesium chloride, or butylmagnesium chloride, or magnesium compound by formula (X) RdMgRd, where Rd is butyl, in inert solvent, followed by conducting interreaction between product obtained and maleimide compound by formula (IX) , where X is halogen, and Y as above, in inert solvent.
EFFECT: improved method for indolo-pyrrolo-carbazole production.
15 cl, 68 ex, 12 tbl
SUBSTANCE: method involves catalytic telomerisation of butadiene with diethylamine in the presence of a catalyst based on cationic complexes of palladium (II) of general formula [(acac)Pd(L)2]BF4 (where acac is an acetylacetonate ligand, L=PPh3, P'Pr3, P"Bu3 P(p-Tol)3 or (L)2=diphosphine ligands, selected from bis(diphenylphosphino)methane(dppm), bis(diphenylphosphino)propane(dppp), bis(diphenylphosphino)butane(dppb), bis(diphenylphosphino)ferrocene(dppf)). The process is carried out in a substrate medium, specifically diethylamine and butadiene, at temperature of 50-90°C. The method enables to obtain N,N-diethylocta-2,7-diene-1-amine with selectivity of 99.9% from the overall mixture of reaction products with high process output which reaches 4180 g of product per 1 g Pd. The catalysts used are more readily available compared to those previously used for the process.
EFFECT: improved method.
1 tbl, 1 ex
SUBSTANCE: invention relates to the field of organic chemistry, in particular to a method of obtaining alkylethers of 1- and 2-naphthalenecarboxylic acids, which are used in the synthesis of herbicides, plant growth hormones, dyes, photomaterials and polymers. The method of obtaining compounds of formula (1a-b) or (2a-b) in which R=CH3, C2H5, n-C3H7,consists in the fact that naphthalene is subjected to interaction with CCl4 and alcohol (methanol, ethanol, n-propanol) in the presence of metallic iron, activated HCl, and acetylacetone with the molar ratio of [Fe0(met.)]:[acetylacetone]:[naphthalene]:[CCl4]:[alcohol]=5-50:5:100:100-1000:100-1000, at a temperature of 130°C for 4-12 h in the argon atmosphere.
EFFECT: total output of alkyl ethers of 1- and 2-naphthalenecarboxylic acids reaches 75%.
1 tbl, 21 ex
SUBSTANCE: invention relates to a method of producing pentacyclo[8.4.0.03.7.04.14.06.11]tetradeca-8,12-diene of formula The method is characterised by catalytic dimerisation of 1,3,5-cycloheptatriene (CHT). The catalyst used is Ni(acac)2-Et2AlCl. The reaction is carried out with molar ratio CHT:Ni(acac)2:Et2AlCl=10:(0.1-0.3):4, in an argon atmosphere, at 20-100°C, in benzene for 8-48 hours.
EFFECT: method enables to obtain the end product separately.
7 ex, 1 tbl
SUBSTANCE: present invention relates to a method of preparing a catalyst complex of formula , where R1, R2, R3 and R4 are independently selected from a group consisting of hydrogen, C1-C20alkyl, C2-C20alkoxy group, halogen and amino group, where if R1 or R3 is an amino group, the amino group is optionally substituted with one or more fragments which are alkyl, if R2 or R4 is an amino group, the amino group is optionally substituted with one or more fragments which are C1-C20alkyl. The method includes a step of reacting a ruthenium catalyst precursor with one or two bidentate ligands of the Schiff base class in a nonpolar solvent and in the presence of a weak base, where the bidentate ligands of the Schiff base class are independently in amount of 1.0-3.0 equivalents relative to the amount of the catalyst precursor (formulae of the precursors and ligands are given in claim 1 of the invention). The invention also discloses a catalyst complex, a supported catalyst for metathesis of olefins and use thereof in olefin metathesis reactions.
EFFECT: invention enables to obtain a catalyst having high activity after activation, monomer stability and a simple and cheap method.
11 cl, 2 tbl
SUBSTANCE: invention relates to method of obtaining bis-(endo-bicyclo[4.2.1]none-2,4-dienes) of general formula (1), n = 0, 1, 2, 4. α,ω-diallenes of general formula interact with 1,3,5-cycloheptatriene (CHT) in presence of catalytic system TiCl4-Et2AlCl, with molar ratio α,ω-diallene:CHT:TiCl4:Et2AlCl = (9-11):20:(0.1-0.3):4, temperature 20-80°C, in benzene, for 10-48 h.
EFFECT: application of claimed invention makes it possible to obtain target compounds.
11 ex, 1 tbl
SUBSTANCE: invention relates to catalyst for purification of gas emissions from nitrogen and carbon (II) oxides, which contains complex of transition metal, applied on aluminium oxide carrier. As transition metal selected is complex copper compound - 3-(2-hydroxybenzoyl)-2H-chromen-2-one, solution of which is used to soak carrier, with the following content of components, wt %: complex copper compound - 3-(2-hydroxybenzoyl)-2H-chromen-2-one - 0.1-0.3; aluminium oxide - the remaining part.
EFFECT: ensuring complete neutralisation of gas emissions from toxic admixtures of nitrogen and carbon oxides, with simplification of preparation technology.
1 tbl, 1 dwg, 5 ex
SUBSTANCE: invention relates to the method of producing alkyl ethers of 4-biphenylcarboxylic acid where R = Me, Et, Prn, which are used as starting compounds for the preparation of medicaments and thermotropic polymers. The essence of the method consists in the interaction of biphenyl with carbon tetrachloride and alcohols (MeOH, EtOH, PrnOH) in the presence of a catalyst selected from the series Fe(acac)3, Fe(OAc)2, Fe(OAc)2*4H2O, FeCl2 and Fe2(CO)9, at 130-150°C for 4-10 hours at a molar ratio of [Fe]: [biphenyl]:[CCl4]:[ROH]=5-20:100:100-2000:100-2000. The following ratios of the catalyst and the reagents [Fe]:[biphenyl]:[CCl4]:[RON]=10:100:1000:1000, at a temperature of 130°C for 8 hours at a temperature of 130°C and a reaction time of 8 hours, the yield of methyl 4-biphenylcarboxylic acid is 41%, ethyl 4-biphenylcarboxylic acid - 14%, propyl ether - 90%.
EFFECT: method improvement.
1 tbl, 22 ex
FIELD: industrial organic synthesis.
SUBSTANCE: invention provides catalyst for production of methyl ethyl ketone via oxidation of n-butenes by oxygen and/or oxygen-containing gas, which catalyst is composed of aqueous solution of molybdeno-vanado-phosphoric heteropolyacid or mixture of the latter with its salt and 5·10-4 to 1·10-2 M palladium stabilized by phthalocyanine ligand at palladium-to-phthalocyanine molar ratio 0.5-2. Mo-V-phosphoric heteropolyacid is depicted by formula H19P3Mo18V7O84. concentration of vanadium being 0.4 to 2.2 g-atom/L. Oxidation of n-butenes is carried out continuously in two steps at temperature 15 to 90оС. Catalyst is regenerated in contact with oxygen or oxygen-containing gas at 140-190оС and oxygen pressure 1-10 gauge atm.
EFFECT: enhanced process efficiency due to increased stability of catalyst components.
7 cl, 1 dwg, 6 tbl, 7 ex